KR100691543B1 - New material for transporting electron and organic electroluminescent display using the same - Google Patents

Abstract

The present invention relates to a material of a novel electron injection transport layer and an organic light emitting device using the same, which can greatly improve the lifespan and efficiency of the organic light emitting device, and a novel in which one or two hetero functional groups are introduced at four substitution sites of anthracene. It provides an organic light emitting device comprising a material of, and an organic compound layer containing the same.

Organic light emitting device, electron injection transport layer, anthracene, hetero functional group, organic compound layer

Description

New material for electron transport and organic light emitting device using same {NEW MATERIAL FOR TRANSPORTING ELECTRON AND ORGANIC ELECTROLUMINESCENT DISPLAY USING THE SAME}

1 is a cross-sectional view showing an example of an organic electroluminescent device.

Reference numeral 1 denotes a substrate, 2 an anode, 3 a hole injection layer, 4 a hole transport layer, 5 an organic light emitting layer, 6 an electron transport layer, and 7 a cathode.

The present invention relates to a material of a novel electron injection transport layer and an organic light emitting device using the same, which can greatly improve the lifetime and efficiency of the organic light emitting device.

An electroluminescent device is defined as a light emitting device using electroluminescence of a solid fluorescent material, and inorganic electroluminescent devices using inorganic materials as light emitters have been put to practical use. However, the inorganic electroluminescent device has a high voltage of more than 100 V and is difficult to emit blue light, making it difficult to make full colors by three primary colors of RGB (red, green, blue).

On the other hand, research on the electroluminescent device using organic materials has also been focused and reviewed for a long time, but due to the low luminous efficiency, practical research has not progressed much. The organic light emitting device uses a principle that electrons and holes injected through a cathode and an anode form excitons in an organic thin film made of a single molecule or a polymer, and light of a specific wavelength is generated from the formed excitons. It was first discovered from single crystals of anthracene. Then, in 1987, Kodak's Tang proposed an organic electroluminescent device having a laminated structure of a functional separation type in which an organic material was divided into two layers, a hole transport layer and a light emitting layer. It was confirmed that a high luminous luminance of more than / m 2 was obtained (Tang, CW; Van Slyke, SA Appl. Phys. Lett . 1987, 51 , 913.). Since then, the organic electroluminescent device is suddenly attracting attention, and research on an organic electroluminescent device having a laminated structure of the same function separation type is being actively conducted.

The structure of a general organic electroluminescent device is a substrate (1), an anode (2), a hole injection layer (3) for receiving holes from the anode, a hole transport layer (4) for transporting holes, holes and electrons as shown in FIG. Is composed of a light emitting layer 5 which combines and emits light, an electron transport layer 6 which receives electrons from the cathode and delivers the light to the light emitting layer, and a cathode 7. In some cases, a light emitting layer may be formed by doping a small amount of fluorescent or phosphorescent dye into the electron transporting layer 6 or the hole transporting layer 4 without a separate light emitting layer 5. One polymer may simultaneously perform the roles of (4), the light emitting layer 5, and the electron transporting layer 6. The organic thin film layers between the two electrodes are formed by vacuum deposition or spin coating, inkjet printing, roll coating, or the like, and a separate electron injection layer may be inserted to efficiently inject electrons from the cathode.

The reason why the organic electroluminescent device is manufactured in a multi-layered thin film structure is to stabilize the interface between the electrode and the organic material or in the case of organic materials, because the movement speed of the holes and the electrons varies greatly. This is because the electrons can be effectively transferred to the light emitting layer and the light emission efficiency can be increased by balancing the density of holes and electrons in the light emitting layer.

As a hole injection material for injecting holes, a compound having excellent thermal stability while maintaining a stable interface with the positive electrode is used. A representative example is copper phthalocyanine, a porphyrin-based copper complex disclosed in US Pat. No. 4,356,429. phthalocyanine, hereinafter referred to as CuPc). Since CuPc is the most stable hole injecting layer, it has been widely used, but it is a problem when manufacturing a full color display due to its strong absorption in the red region.

The organic monomolecular material for the hole transport layer is typically an arylamine based material having high hole transport speed and excellent electrical stability. In order to increase the thermal stability of the arylamine-based material, a hole transport material introducing a naphthyl substituent or a spiro group has been reported (US Pat. Nos. 5,554,459 and 5,840,217).

Early hole transport layer organic materials are commonly referred to as N, N'-diphenyl-N, N'-bis (3-methylphenyl) -1,1'-diphenyl-4,4'-diamine (hereinafter referred to as TPD). N-naphthyl-N-phenyl-1,1'-diphenyl-4,4'-diamine (hereinafter referred to as NPD) series or more aromatic groups, which have been used but are unstable at temperatures above Substituted amines are used. In addition, an arylamine compound containing a spiro compound published by Covion, an arylamine compound containing a perylene released by Motorola (US Pat. No. 6,013,383), US Pat. No. 6,150,043 Azacycloheptatriene compound disclosed in the present invention, bis (diphenylvinylphenyl) anthracene disclosed by Kodak Corporation and published in Korean Patent Publication No. 2000-48006, silicon germanium oxide compound disclosed in US Pat. No. 6,249,085, Materials for hole transport layers, such as silicon-based arylamine compounds and fused compounds containing nitrogen atoms, disclosed in Japanese Patent Application Laid-Open Nos. 2001-172284 and 2001-172280 have been reported. In particular, since the hole transport layer organic monomolecular material has to have a fast hole moving speed and forms an interface in contact with the light emitting layer, it is very important that the ionization potential has an appropriate value between the hole injection layer and the light emitting layer in order to suppress the generation of the excitons of the hole transport layer and the light emitting layer. It is important. Another function requires the ability to properly control the electrons moving in the light emitting layer. Therefore, the smaller the electron affinity, the better the characteristics.

The organic monomolecule for the light emitting layer, in which holes and electrons combine to emit light, is largely divided into a host material and a guest material in terms of function. In general, the host or guest material can emit light alone, but the efficiency and brightness are low, and because of the self-packing phenomenon of the same molecules, each of the molecules exhibits the characteristics of the excimer rather than the characteristics of each molecule. Not desirable Therefore, a small amount of doping of the guest to the host can compensate for these problems.

First, 8-hydroxyquinoline aluminum salt (Alq3) is most commonly used as a green light emitting layer, and derivatives of quinacridone, coumarine, etc. are used to increase efficiency. Doped materials with high quantum efficiency, such as derivatives, are used.

The organic materials for the blue light emitting layer have problems of low melting point and light emission stability at the initial state and short lifespan, compared to Alq3, which is a green light emitter. In addition, since most of the materials for the blue light emitting layer are light blue rather than pure blue, they are still unsuitable for full-color display, and doped with perylene to improve luminous efficiency as in the case of green. Representative organic materials for blue light emitting layers include aromatic hydrocarbons, spiro-type materials, organometallic compounds including aluminum, heterocyclic compounds with imidazole groups, and fused aromatic compounds, which are described in US Patent No. 5,516,577. 5,366,811, 5,840,217, 5,150,006 and 5,645,948.

In the case of the red light emitting layer, a small amount of the red light emitting material is doped into Alq3, which is a large amount of green light emitting material due to the characteristics of the red light having a small band gap, but device stability and high driving voltage have been raised as problems. As another approach, a device may be manufactured using a fluorescent polymer that simultaneously plays a role of hole transport and light emission without a separate hole transport layer.

As organic monomolecular materials for the electron transport layer, organometallic complexes having excellent electron stability and electron transfer speed are good candidates. Among them, Alq3 having excellent stability and high electron affinity has been reported to be the most excellent. However, when used in a blue light emitting device, color purity is degraded due to emission due to exciton diffusion. In addition, conventionally known materials for electron transport include flavon derivatives published by Sanyo or germanium and silicon cyclopetadiene derivatives from Chisso (Japanese Patent Publication No. 1998-017860). Japanese Patent Application Laid-Open No. 1999-087067).

Meanwhile, Professor Thomson of the University of Southern California and Professor Forest of the University of Princeton have phenylpyridine iridium in host materials such as PBD (full name), TAZ (full name) or TPBI (full name), which have high electron affinity and excellent electron transport ability. Doping organic phosphors such as to obtain a high efficiency device (C. Adachi, MA Baldo, and SR Forrest, Applied Physics Letter , 77 , 904, 2000., C. Adachi, MA Baldo, SR Forrest, S. Lamansky, ME Thompsom, and RC Kwong, Applied Physics Letter , 78 , 1622, 2001). This result is an example of overcoming the limit efficiency caused by the singlelet-singlet transition to the triplet-singlet transition, and for the new electron injection and transport disclosed in the present invention. When applied to the material it will be possible to obtain an organic electroluminescent device having a much higher luminous efficiency and long life.

The organic light emitting device using the appropriate organic monomolecular materials for each layer has problems of short light emitting life, low durability, and low reliability. These causes include physical, chemical changes, photochemical and electrochemical changes of organic materials, oxidation of cathodes, delamination and melting, crystallization and pyrolysis of organic compounds.

Therefore, the organic electroluminescent device can obtain an arbitrary emission color by changing the structure of an appropriate organic monomolecular material and various high efficiency organic electroluminescent devices have been proposed by the host guest system, but it is satisfactory when used at the practical level. It lacks luminance characteristics, lifetime and durability.

Disclosure of Invention It is an object of the present invention to provide a novel electron injection and transport layer material and an organic electroluminescent device using the same, which can considerably improve the luminous efficiency, stability and device life.

Another object of the present invention is to provide a material having thermal stability and sublimation necessary for a vacuum deposition process and an organic electroluminescent device using the same.

The present invention, in order to achieve the above object, a compound represented by the following formula (1), a compound represented by the formula (2), a compound represented by the formula (3), a compound represented by the formula (4), and a compound represented by the formula (5) Provides:

[Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the formula 1, 2, 3, 4, and 5,

R ¹ and R ² are each independently or simultaneously a group derived from a hydrogen atom, an aliphatic hydrocarbon having 1 to 20 carbon atoms, phenyl, naphthyl, biphenyl, anthracenyl, aromatic heterocycle, or aromatic ring assembly, wherein R At least one of ¹ , and R ² is a group derived from phenyl, naphthyl, biphenyl, aromatic heterocycle or aromatic ring assembly,

Ar is a group derived from phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocycle or an aromatic ring assembly,

R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aliphatic hydrocarbon, substituted phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocyclic or aromatic ring assembly,

X is NR ⁴ , sulfur atom or oxygen atom,

R ⁴ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aliphatic hydrocarbon, phenyl, naphthyl, biphenyl, anthracenyl, or a group derived from an aromatic heterocycle or an aromatic ring assembly.

In addition, the present invention is a compound represented by Formula 1, a compound represented by Formula 2, a compound represented by Formula 3, a compound represented by Formula 4, and a compound represented by the compound represented by Formula 5 An organic light emitting device including an organic compound layer containing the organic compound selected above is provided.

Hereinafter, the present invention will be described in detail.

The present invention is contained in the organic compound layer of the organic electroluminescence (organic EL) device, an electroluminescent device, one to two at four substitution sites of anthracene, which can improve luminous efficiency, lifetime, and low voltage driving. A novel material into which a hetero functional group is introduced and an organic light emitting device containing the material in an organic compound layer are provided.

First, the structure of the organic light emitting device to which the novel material of the present invention can be applied will be described.

1 is a cross-sectional view showing an example of a structure that can be applied to the organic electroluminescent device of the present invention, 1 is a substrate, 2 is an anode, 3 is a hole injection layer, 4 is a hole transport layer, 5 is an organic light emitting layer, 6 Silver electron transport layer, 7 represents a cathode, respectively.

The substrate 1 is a support of an organic electroluminescent device, and a silicon wafer, quartz or glass plate, metal plate, plastic film or sheet, or the like can be used.

The anode 2 is positioned on the substrate 1. The anode 2 injects holes into the hole injection layer 3 positioned thereon, and a work function of metals such as aluminum, gold, silver, nickel, palladium, platinum, indium tin oxide, indium zinc oxide, and the like. A large substance may be used, and a conductive polymer such as carbon black, polythiophene, polypyrrole, or polyaniline may also be used.

The hole injection layer 3 is positioned on the anode 2. The condition required for the material of the hole injection layer 3 is high hole injection efficiency from the anode, it should be able to transport the injected holes efficiently. This requires a small ionization potential, high transparency to visible light, and excellent hole stability.                     

The hole transport layer 4 is positioned on the hole injection layer 3. The hole transport layer 4 receives holes from the hole injection layer 3 and transports the holes to the organic light emitting layer 5 positioned thereon, and serves to prevent high hole mobility, hole stability, and electrons. In addition to these general requirements, when applied for vehicle body display, heat resistance to the device is required, and a material having a glass transition temperature (Tg) of 70 ° C. or higher is preferable. Materials satisfying these conditions include NPD (or NPB), spiro-arylamine compounds, perylene-arylamine compounds, azacycloheptatriene compounds, bis (diphenylvinylphenyl) anthracene, silicon germanium oxide Compounds, silicone arylamine compounds and the like.

The organic light emitting layer 5 is positioned on the hole transport layer 4. The organic light emitting layer 5 is a layer in which holes and electrons injected from the anode 2 and the cathode 7, respectively, recombine to emit light, and are made of a material having high quantum efficiency.

Alq3 for green, Balq (8-hydroxyquinoline beryllium salt), DPVBi (4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl) for green Series, Spiro substance, Spiro-DPVBi (Spiro-4,4'-bis (2,2-diphenylethenyl) -1,1'-biphenyl), LiPBO (2- (2-benzoxazoyl) -phenol lithium salt) , Bis (diphenylvinylphenylvinyl) benzene, aluminum-quinoline metal complexes, metal complexes of imidazole, thiazole and oxazole, and the like, perylene, and BczVBi (3,3 '[( 1,1'-biphenyl) -4,4'-diyldi-2,1-ethenediyl] bis (9-ethyl) -9H-carbazole; DSA (distrylamine) can be used by doping in small amounts. In the case of red, DCJTB ([2- (1,1-dimethylethyl) -6- [2- (2,3,6,7-tetrahydro-1,1,7,7-tetramethyl-1H, 5H A small amount of doping such as -benzo (ij) quinolizin-9-yl) ethenyl] -4H-pyran-4-ylidene] -propanedinitrile) is used. When forming a light emitting layer using a process such as inkjet printing, roll coating, or spin coating, a polymer such as polyphenylene vinylene (PPV) -based polymer or poly fluorene may be added to the organic light emitting layer 5. Can be used.

The electron transport layer 6 is positioned on the organic light emitting layer 5. The electron transport layer 6 needs a material having high electron injection efficiency from the cathode 7 positioned thereon and capable of efficiently transporting the injected electrons. To this end, it must be made of a material having high electron affinity and electron transfer speed and excellent stability to electrons. As a material satisfying such conditions, aromatic compounds such as tetraphenyl butadiene (Japanese Patent Laid-Open No. 57-51781) and metal complexes such as aluminum of 8-hydroxy quinoline (Japanese Patent Laid-Open No. 59-194393) ), A metal complex of 10-hydroxy benzo [h] quinoline (Japanese Patent Laid-Open Publication No. Hei 6-322362), a cyclopentadiene derivative (Japanese Laid-Open Patent Publication No. Hei 2-289675), a bis styryl benzene derivative (Japanese Laid Open) Japanese Patent Application Laid-Open No. 1-245087, and Japanese Patent Application Laid-Open No. 2-222484), a perylene derivative (Japanese Patent Application Laid-Open No. 2-189890, and Japanese Patent Application Laid-Open No. 3-791), p-phenylene Derivatives (Japanese Patent Application Laid-open No. Hei 3-33183), oxazole derivatives (Japanese Patent Laid-Open No. H11-345686) and the like can be used.

The cathode 7 is positioned on the electron transport layer 6. The cathode 7 injects electrons into the electron transport layer 6. As the material used as the cathode, it is possible to use the material used for the anode 2, and a metal having a low work function is more preferable for efficient electron injection. In particular, a suitable metal such as tin, magnesium, indium, calcium, sodium, lithium, aluminum, silver, or a suitable alloy thereof can be used. In addition, an electrode having a two-layer structure such as lithium fluoride and aluminum, lithium oxide and aluminum, strontium oxide and aluminum having a thickness of 100 μm or less may also be used.

Therefore, at least one organic compound layer containing the organic compound represented by Chemical Formulas 1 to 5 according to the present invention is positioned between the anode for injecting holes and the cathode for injecting electrons. As such, by containing the novel material of the present invention in the organic compound layer between the anode and the cathode, preferably in the electron injection and transport layer between the light emitting layer and the cathode, the efficiency and lifespan of the organic electroluminescent device applied can be greatly improved. In addition, it is possible to provide an organic electroluminescent device having low driving voltage and excellent stability. In addition, by adding a suitable dopant (dopant) to the material used in the present invention without a separate light emitting layer, it can be performed at the same time as the electron transport layer and the light emitting layer alone.

The organic compound layer containing the compound represented by Chemical Formulas 1 to 5 of the present invention is particularly an electron injection and transport layer having an electron injection and transport function, an electron injection and light emitting layer having an electron injection and light emission function, or an electron transport and light emission function It is preferable to be an electron transporting and emitting layer having For example, the novel materials of the present invention may form an electron injection and transport layer and other materials may form an emission layer, or the novel materials of the present invention may simultaneously form an electron injection and transport layer and an emission layer.

Among the compounds of Formulas 1 to 5 contained in the organic compound layer of the present invention, a more preferable compound is a compound of Formula 1a or Formula 3a.

[Formula 1a]

[Formula 3a]

In the formula of Formula 1a and Formula 3a,

Ar ₁ , Ar ₂ , and Ar ₃ each independently or simultaneously represent an aromatic hydrocarbon such as benzene, naphthalene, biphenyl, and R ⁵ represents a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon or a heterocyclic compound.

As a conventional material for electron injection and transport layer, many organic monomer materials having imidazole group, oxazole group, and thiazole group have been reported. However, before these materials were reported as electron transporting materials, European Patent Publication No. 0700917 A2 of Motorola had already reported application of metal complex compounds of such materials as organic electroluminescent devices of a blue light emitting layer or a cyan light emitting layer. . Subsequently, U.S. Patent Nos. 5,766,779 and 5,645,948 disclose organic electroluminescent devices in which organic materials having imidazole, thiazole, or oxazole groups are used as the electron transporting layer and the emitting layer, which are disclosed in U.S. Patent No. 5,766,779. Two to eight such hetero functional groups were included in one molecule, and were applied to the electron transport layer of the organic electroluminescent device. In addition, US Pat. No. 5,645,948 applies the same heterofunctional groups to the light emitting layer by using an organic material containing 3 to 8 molecules in one molecule, but in the present invention, 1 to 2 heterofunctional groups are introduced at 4 substitution sites of anthracene. Therefore, it can be said that it is used as a material for electron injection and transport.

TPBI (Formula 6), published by Kodak Corporation in 1996 and disclosed in US Pat. No. 5,645,948, is known as a representative electron transport layer material having an imidazole group, and as shown in the following Formula 6, 1,3,5- It contains three N-phenyl benzimidazole groups in the substitution position and functionally blocks electrons from the light emitting layer as well as the ability to transfer electrons, but has a problem of low stability for practical application.                     

[Formula 6]

In addition, the electron transporting materials disclosed in Japanese Patent Application Laid-Open No. 11-345686 reported that they can be applied to the light emitting layer containing oxazole group and thiazole group as shown in the following Chemical Formulas 7 to 10, but the driving voltage, luminance and It can be seen that it is not sufficient in terms of the lifetime of the device.

[Formula 7]

[Formula 8]

[Formula 9]

[Formula 10]

As can be seen from the prior art, the present inventors synthesized the novel organic materials represented by Chemical Formulas 1 to 5 under the recognition that any organic material except an organometallic complex such as Alq3 was difficult to be used, and the appropriate hole injection layer, After selecting the hole transport layer and the light emitting layer, and applying them to the electron injection and transport layer, the results were much better than the conventional Alq3 in terms of driving voltage, efficiency, device life and thermal stability.

Derivatives of anthracene used by the inventors for the new electron injection and transport layer have been studied in the US, Kodak, TDK, and the like, and have been disclosed in various patents, but the historical origin of anthracene is from the early 1960s. Started. In 1965, Helrich and Pope first announced organic electroluminescence using anthracene single crystals, but they had many problems in practical use because of their low luminous efficiency and high voltage (W. Helfrich, WG Schneider, Phys. Rev. Lett . 14 , 229, 1965. M. Pope, H. Kallmann, J. Giachino, J. Chem. Phys ., 42 , 2540, 1965).

Therefore, in order to develop an excellent organic electroluminescent device, it is very important which functional group is introduced at which position among the 10 reaction substitution sites of anthracene. The anthracene derivatives published by Kodak Corp. and Tidike Corp. are all used for the light emitting layer of the organic electroluminescent device. The anthracene derivative disclosed in Japanese Patent Application Laid-open No. Hei 11-345686 claims that it can be used as a light emitting layer and an electron transporting material, but it is included in the broad claims of the patent, but there is no further mention in the synthesis examples or examples and electron injection has been made so far. And examples of practical use as transporting materials are not found.

In order to overcome this problem, the present inventors use the place of substitution of anthracene 2,6,9,10, while Japanese Patent Laid-Open No. 11-345686 discloses two substitutions of 1,5, 1,8 or 2,6. The location is only used and the 9,10 position is substituted with only hydrogen atoms.

First, the structural characteristics of the compound represented by Chemical Formulas 1 to 5 synthesized by the present inventors are as follows. Anthracene has 10 substitution sites, and the present inventors focused on finding an optimal compound while freely converting 4 substitution sites of 2,6,9,10 of anthracene, and this concept is the biggest feature. That is, at 9,10 positions of anthracene, aromatic hydrocarbons such as phenyl, naphthyl, and biphenyl are substituted, respectively or simultaneously, and at 2,6 positions, imidazole, oxazole and thiazole groups are respectively or simultaneously directly substituted, or phenyl, etc. Substances were synthesized by substituting the imidazole, oxazole and thiazole groups, respectively, or simultaneously after substituting the aromatic hydrocarbons.

When the organic light emitting device is used as a layer containing the electron transporting ability, it was found that the excellent driving voltage and the lifetime of the device are simultaneously improved. Representative materials are described in more detail in the Examples below. Representative materials having electron injection and transport ability of the present invention are the following formula 1-1 to 1-16, formula 2-1 to 2-5, formula 3-1 to 3-9, formula 4-1 to formula 4-5 , Compounds of the formulas 5-1 to 5-5.

[Formula 1-1] [Formula 1-2]

[Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6]                     

[Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

[Formula 1-11] [Formula 1-12]                     

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

[Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

[Formula 3-1] [Formula 3-2]                     

[Formula 3-3] [Formula 3-4]

[Formula 3-5] [Formula 3-6]

[Formula 3-7] [Formula 3-8]

[Formula 3-9]

[Formula 4-1] [Formula 4-2]                     

[Formula 4-3] [Formula 4-4]

[Formula 4-5]

[Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

Examples of the compounds presented above are only a part for the purpose of understanding the present invention, and the compounds provided by the present invention are not limited thereto.

Synthesis method of a compound satisfying Formulas 1, 2, 3, 4, and 5 and an organic electroluminescent device using the same will be described in more detail with reference to Examples and Comparative Examples below. However, the examples are not intended to exemplify the present invention, but are not limited thereto. Compounds satisfying Chemical Formulas 1, 2, 3, 4, and 5, which are not described in the Examples, are also prepared within the same category, and organic light emitting diodes are emitted. It can be contained and applied to the organic compound layer of the device.

EXAMPLE

Starting materials were selected from the compounds of Formulas a to i for the synthesis of the compounds represented by Formulas 1 to 5, and their preparation is shown in Preparation Examples 1 to 9 below.

[Formula a] [Formula b] [Formula c]

[Formula d] [Formula e] [Formula f]

[Formula g] [Formula h] [Formula i]                     

[Formula j] [Formula k]

[Formula 1]

Preparation Example 1

(Preparation of starting material represented by Formula a)

2,6-diaminoanthraquinone (23.8 g, 100 mmol) was dispersed in an aqueous solution of hydrogen bromide at a concentration of 48 wt%, and sodium nitrite (NaNO ₂ , 14.1 g; 204 mmol) was slowly added at 20 ° C. After gas evolution, a solution of copper bromide (CuBr, 29.5 g; 206 mmol) in 48 wt% aqueous hydrogen bromide solution (63 mL) was slowly added with a small amount of ethanol (50 mL). The temperature of the reaction was slowly raised to room temperature and then refluxed for one hour. After cooling to room temperature, water was added, and the resulting precipitate was filtered, washed with water, and dried in vacuo. The obtained solid was dissolved in chloroform, passed through silica gel, and the solvent was removed under reduced pressure. After separation by column chromatography, the mixture was recrystallized with chloroform to obtain a compound of formula a (10 g, yield 27%) as a light yellow starting material.

The analysis results of this compound are as follows.

1 H NMR (300 MHz, CDCl ₃ ), 8.44 (d, J = 2.1 Hz, 2H), 8.18 (d, J = 8.0 Hz, 2H), 7.95 (dd, J = 2.1, 8.0 Hz, 2H.)

Preparation Example 2

(Preparation of starting material represented by Formula b)

In a nitrogen atmosphere, 2-bromo biphenyl (8.83 ml, 51.2 mmol) was dissolved in purified THF (200 ml), cooled to -78 ° C and tertiary-butyllithium (60 ml, 1.7 M pentane solution) was slowly added. Added. After stirring at the same temperature for 40 minutes, the compound of Formula a prepared in Preparation Example 1 (7.50 g; 20.5 mmol) was added at the same temperature. After removing the cooling vessel, the reaction was stirred for 15 hours at room temperature. The reaction solution was slowly added to a mixed solvent of diethyl ether (200 mL) and 2N hydrochloric acid solution (200 mL) and stirred at room temperature for 40 minutes. The resulting precipitate was filtered and washed well with water and ethyl ether. This material was dried in vacuo to give the compound represented by compound b (11.8 g, yield 85%).

Preparation Example 3

(Preparation of starting material represented by Formula c)

A compound of the compound represented by Formula b prepared in Preparation Example 2 (4.00 g; 5.93 mmol), potassium iodine (9.85 g; 59.3 mmol) and sodium hypophosphite hydrate (10.44 g, 98.0 mmol) was prepared by ortho-dichloro It was refluxed for 24 hours in a mixed solution of benzene (600 mL) and acetic acid (80 mL). After cooling to room temperature, the mixture was extracted with chloroform, water was removed with anhydrous magnesium sulfate, and the solvent was removed under reduced pressure. The obtained solid was dissolved in chloroform, passed through a short silica gel column, and the solvent was removed under reduced pressure. The mixture was dispersed in normal-hexane, stirred, filtered, and dried in vacuo to obtain a compound (3.3 g, yield 87%) represented by light yellow (C).

The analysis results of this compound are as follows.

Melting point 478.1 C; 1 H NMR (300 MHz, CDCl 3) 7.92 (d, J = 7.6 Hz, 4H), 7.46 (t, J = 8.0 Hz, 4H), 7.33 (t, J = 7.4 Hz, 4H), 7.21 (d, J = 7.6 Hz, 4H), 6.88 (dd, J = 2.1, 8.6 Hz, 2H), 6.47 (d, J = 2.1 Hz, 2H), 6.22 (d, J = 8.6 Hz, 2H); MS (M +) 636; Anal. Calcd for C ₃₈ H ₂₂ Br ₂ : C, 71.50; H, 3.47; Br, 25.03. Found: C, 71.90; H, 3. 40; Br, 25.7.

Preparation Example 4

(Preparation of starting material represented by Formula d)

Copper bromide (CuBr ₂ , 18.0 g, 80.0 mmol) and tertiary-butyl nitrite (12 mL, 101 mmol) were dispersed in acetonitrile (250 mL) at 65 ° C. and stirred, followed by 2-aminoanthraquinone (15.0 g, 67.2 mmol) was added slowly dropwise over 5 minutes. After the generation of gas, the reaction solution was cooled to room temperature, and the reaction solution was added to 20 wt% aqueous hydrochloric acid solution (1000 mL) and extracted with dichloromethane. The organic layer was dried over anhydrous magnesium sulfate, followed by removal of residual moisture. Separation by column chromatography (dichloromethane / n-hexane = 4/1) to give a compound of the light yellow formula (14.5 g, yield 75%).

The analysis results of this compound are as follows.

Melting point 207.5 C; 1 H NMR (500 MHz, CDCl 3) 8.43 (d, J = 1.8 Hz, 1H), 8.30 (m, 2H), 8.17 (d, J = 8.3 Hz, 1H), 7.91 (dd, J = 1.8, 8.3 Hz, 1H), 7.82 (m, 2 H); MS (M +) 286; Anal. Calcd for C ₁₄ H ₇ BrO 2: C, 58.57; H, 2. 46; Br, 27.83; O, 11.14. Found: C, 58.88; H, 2.39; Br, 27.80; O, 10.93.

Preparation Example 5

(Preparation of starting material represented by Formula e)                     

2-bromobiphenyl (9.0 mL, 52 mmol) was dissolved in tetrahydrofuran (100 mL) dried under nitrogen atmosphere, and tertiary-butyllithium (40 mL, 1.7 M pentane solution) was slowly added at -78 ° C. After stirring at the same temperature for one hour, the compound represented by Chemical Formula d prepared in Preparation Example 4 (4.9 g, 17 mmol) was added thereto. After removing the cooling vessel and stirred for 3 hours at room temperature. An aqueous ammonium chloride solution was added to the reaction mixture, followed by extraction with methylene chloride. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. The resulting solid was dispersed in ethanol, stirred for one hour, filtered and washed with clean ethanol. After drying, a compound represented by the formula (e) (9.50 g, yield 94%) was obtained.

Preparation Example 6

(Preparation of starting material represented by Formula f)

After dispersing the compound represented by Chemical Formula e (6.0 g, 10.1 mmol) prepared in Preparation Example 5 in 300 ml of acetic acid under nitrogen atmosphere, potassium iodine (16.8 g, 101 mmol) and sodium hypophosphite hydrate (17.7 g) 167 mmol) was added and stirred with boiling for 3 hours. After cooling to room temperature, the mixture was filtered, washed with water and methanol and dried in vacuo to obtain a compound (5.0 g, yield 88%) represented by the light yellow formula f.

Preparation Example 7

(Preparation of starting material represented by Chemical Formula g)

To 100 ml of acetic acid was dispersed the compound represented by the formula (e) prepared in Preparation Example 5 (9.5 g, 16 mmol), and 5 drops of concentrated sulfuric acid was added thereto and refluxed for 3 hours. After cooling to room temperature, the resulting solid was filtered, washed with clean acetic acid, and then washed with water and ethanol. After drying, the product was purified by sublimation to obtain a compound represented by the formula g as a white solid (8.0 g, 89% yield).

Preparation Example 8

(Preparation of starting material represented by Formula h)

After completely dissolving the compound represented by Chemical Formula g (10 g, 17.9 mmol) prepared in Preparation Example 7 in 150 mL of purified THF under a nitrogen atmosphere, tertiary-butyllithium (31.5 mL, 1.7 M at -78 ° C) was dissolved. Pentane solution) was added slowly. After stirring for one hour at the same temperature, trimethylborate (8 mL, 71.5 mmol) was added. The cold vessel was removed and the reaction mixture was stirred at room temperature for 3 hours. 2N aqueous hydrochloric acid solution (100 mL) was added to the reaction mixture, which was stirred for 1.5 hours at room temperature. The resulting precipitate was filtered off, washed successively with water and ethyl ether, and dried in vacuo. After drying, the mixture was dispersed in ethyl ether, stirred for 2 hours, filtered, and dried to obtain a white compound (7.6 g, yield 81%).

Preparation Example 9

(Preparation of starting material represented by Formula i)

2-bromonaphthalene (11 g, 53.12 mmol) was dissolved in tetrahydrofuran (100 mL) dried under a nitrogen atmosphere, and tertiary-butyllithium (47.0 mL, 1.7 M pentane solution) was slowly added at -78 ° C. After stirring at the same temperature for one hour, Compound (6.31 g, 22 mmol) represented by Chemical Formula d prepared in Preparation Example 4 was added thereto. After removing the cooling vessel and stirred for 3 hours at room temperature. An aqueous ammonium chloride solution was added to the reaction mixture, followed by extraction with methylene chloride. The organic layer was dried over anhydrous magnesium sulfate and the solvent was removed. A small amount of ethyl ether was dissolved in the obtained mixture, and petroleum ether was added thereto, followed by stirring for several hours to obtain a solid compound. After filtration and drying in vacuo, pure naphthyldialcohol (11.2 g, yield 94%) was obtained.

Dinaphthyldialcohol (11.2 g, 20.5 mmol) was dispersed in 200 ml of acetic acid under nitrogen atmosphere, and then potassium iodine (34.2 g, 210 mmol) and sodium hypophosphite hydrate (37 g, 340 mmol) were added for 3 hours. Stir while boiling. After cooling to room temperature, the mixture was filtered, washed with water and methanol and dried in vacuo to obtain a compound (7.2 g, yield 64%) represented by the formula (I) in light yellow color.

Example 1

(Production of Compound Represented by Formula 2-3)

Dissolve 4-bromophenylaldehyde (41.6 g, 225 mmol) and 1,3-propanediol (16.31 ml, 225 mmol) in 500 ml of toluene, add 1 g of para-toluenesulfonic acid and remove water to reflux for two days. I was. 100 ml of ether was added to the reaction mixture and diluted, and then 100 ml of water was poured out and extracted. The liquid obtained by removing the organic solvent was separated by column chromatography, and crystals were formed by petroleum ether in the obtained liquid to obtain 4-bromophenylacetal as a white solid (45 g, yield 82%).

100 mL of purified THF was added to 4-bromophenyl acetal (5.00 g, 20.6 mmol), and completely dissolved, and the reaction temperature was lowered to -78 ° C. Tertiary-butyllithium (1.7 M pentane solution, 24.2 mL, 41.1 mmol) was slowly added thereto, followed by stirring for 1 hour. Trimethylborate (7 mL, 62.4 mmol) was slowly injected at −78 ° C., and then the reaction temperature was slowly raised and stirred at room temperature for 3 hours.

The reaction was poured into 200 mL of 2N hydrochloric acid aqueous solution, stirred for 1 hour, filtered, washed with water and petroleum ether, and dried to obtain white 4-formylphenylboronic acid (2.5 g, 81% yield).

The compound represented by Formula c prepared in Preparation Example 3 (0.4 g, 0.62 mmol) and 4-formylphenylboronic acid (1.1 g, 7.34 mmol) were added to a solution of 10 ml of 2 N potassium carbonate solution and 30 ml of toluene. Pd (PPh ₃ ) ₄ (0.16 g, 0.14 mmol) was added thereto while stirring, and the mixture was refluxed for 3 days. The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. The solid compound was washed with 40 ml of ethanol, filtered and recrystallized with chloroform to obtain dialdehyde (155 mg, yield 36%).

Dialdehyde (120 mg, 0.17 mmol) and N-phenyl-1,2-phenylenediamine (82 mg, 0.45 mmol) were added to 20 ml of toluene and 10 ml of acetic acid, refluxed for 2 days, and the temperature was lowered to room temperature. After filtration and washed with ethanol. The obtained solid was washed with 100 ml of chloroform and filtered to obtain a clean compound (120 mg, yield 68%) represented by Chemical Formula 2-3.

The analysis results of this compound are as follows.

Melting point 395.0 ° C .; 1 H NMR (300 MHz, CDCl ₃ ) 7.88 (2H), 7.62 (2H), 7.66-7.60 (10H), 7.55-7.44 (15H), 7.40 (2H), 7.38-30 (9H), 6.95 (6H), 6.83 (4 H); MS [M + H] 1019.

Example 2

(Production of Compound Represented by Formula 1-2)

Compound (1.00 g, 1.80 mmol) and 4-formylphenylboronic acid (0.74 g, 4.93 mmol) represented by Chemical Formula f prepared in Preparation Example 6 were added to a solution of 20 ml of 2N aqueous potassium carbonate solution and 40 ml of toluene. Pd (PPh ₃ ) ₄ (0.20 g, 0.17 mmol) was added thereto while stirring and refluxed for 3 days. The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Washed with 100 ml of ethanol, filtered and recrystallized with ethyl acetate to obtain anthracene phenylaldehyde (330 mg, 31% yield).

40 ml of toluene and 10 ml of acetic acid were refluxed in anthracene phenylaldehyde (0.33 g, 0.56 mmol) and N-phenyl-1,2-phenylenediamine (0.11 g, 0.60 mmol). After reacting for 2 days, the mixture was cooled to room temperature, the solid formed was filtered, washed with ethanol and chloroform, and filtered to obtain a compound represented by Chemical Formula 1-2 (120 mg, yield 28%).

The analysis results of this compound are as follows.

1 H NMR (300 MHz, CDCl ₃ ) 7.89 (1 H), 7.75 (1 H), 7.62-7.29 (24 H), 6.98-6.76 (12H); MS [M + H] 751.

Example 3

(Production of Compound Represented by Formula 1-4)

Compound (4.00 g, 7.85 mmol) and 4-formylphenylboronic acid (3.53 g, 23.5 mmol) represented by Formula (I) prepared in Preparation Example 9 were added to a solution of 20 ml of 2N potassium carbonate aqueous solution and 60 ml of toluene. Pd (PPh ₃ ) ₄ (0.27 g, 0.23 mmol) was added thereto while stirring and refluxed for 3 days. The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, passed through a silica gel layer, and the solvent was removed to obtain a solid compound. Washed with 100 ml of ethanol, filtered and recrystallized with ethyl acetate to give anthracene phenylaldehyde (2.00 g, yield 47.6%).

To anthracene phenylaldehyde (2 g, 3.74 mmol) and N-phenyl-1,2-phenylenediamine (0.69 g, 3.74 mmol), 40 ml of toluene and 10 ml of acetic acid were added to reflux. After reacting for 2 days, the mixture was cooled to room temperature and the solid formed was filtered, washed with ethanol and chloroform, and filtered to obtain a compound represented by Chemical Formula 1-4 (1.3 g, yield 49.7%).

The analysis results of this compound are as follows.

Melting point 352.0 ° C .; 1 H NMR (300 MHz, CDCl ₃ ) 8.28 (s, 2H), 8.14 (d, 2H), 7.99 (t, 4H), 7.81 (t, 4H), 7.62 (m, 4H), 7.53 (d, 2H) , 7.45 (m, 4H), 7.32-7.26 (m, 6H), 7.22 (s, 6H); MS [M + H] 699.

Example 4

(Production of Compound Represented by Formula 2-4)

2-bromo naphthalene (5.78 g, 28.0 mmol) was dissolved in purified THF (40 mL) under nitrogen atmosphere, cooled to -78 ° C, and tert-butyllithium (21 mL, 1.7 M pentane solution) was added slowly. . After stirring at the same temperature for 40 minutes, the compound represented by Chemical Formula a (2.93 g, 8.00 mmol) prepared in Preparation Example 1 was added at the same temperature. After removing the cooling vessel, the reaction was stirred at room temperature for 3 hours. Ammonium chloride solution (40 mL) was slowly added to the reaction solution, and the mixture was stirred at room temperature for 40 minutes. The resulting precipitate was filtered and washed well with water and petroleum ether. This material was dried in vacuo to give a dialcohol (4.10 g, yield 82%).

A mixture of dialcohol (4.10 g, 6.59 mmol), potassium iodine (10.94 g, 65.9 mmol) and sodium hypophosphite hydrate (11.6 g, 109 mmol) was refluxed in acetic acid (200 mL) for 24 hours. Cabinet, filtered and washed with acetic acid, water, petroleum ether in turn and dried to give 2,6-dibromo-9,10- dinaphthalen-2-yl-anthracene (3.15 g, 81% yield).

2 ml of 2 N aqueous potassium carbonate solution with 2,6-dibromo-9,10-dinaphthalen-2-yl-anthracene (3.15 g, 5.35 mmol) and 4-formylphenylboronic acid (2.81 g, 18.7 mmol) Pd (PPh ₃ ) ₄ (0.25 g, 0.22 mmol) was added thereto under stirring and 100 mL of toluene, and the mixture was refluxed for 15 hours. The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, and separated by column chromatography to obtain dinaphthyl anthracene phenyldialdehyde (2.77 g, yield 81%).

120 mL of toluene and 60 mL of acetic acid were refluxed in the dinaphthyl anthracene phenyldialdehyde (2.77 g, 4.34 mmol) and N-phenyl-1,2-phenylenediamine (2.00 g, 10.9 mmol). After reacting for 15 hours, manganese oxide (1.51 g, 17.4 mmol) was added thereto, followed by further reaction for 2 hours, and then the temperature was reduced to room temperature. The solid formed was filtered, washed with ethanol and chloroform, and filtered to obtain a compound represented by Chemical Formula 2-4. (1.52 g, yield 36%) was obtained. The melting point of this compound is 487.4 ° C.

Example 5

(Preparation of a compound represented by Formula 1-14)

10 mL of 2 N potassium carbonate with 9,10-bis-biphenyl-2-yl-2,6-dibromoanthracene (1.00 g, 3.55 mmol) and 4-formylphenylboronic acid (0.81 g, 3.90 mmol) Pd (PPh ₃ ) ₄ (0.10 g, 0.09 mmol) was added thereto under stirring and 30 mL of toluene, followed by reflux for 2 days.

The toluene layer was extracted, washed with water, dried over anhydrous magnesium sulfate, the solvent was removed and the resultant was separated by column chromatography (CHCl ₃ / HEX = 1/2) to obtain the desired 4- (9,10-bis-biphenyl-2-yl. 0.8 g of -6-bromo-anthracen-2-yl) -benzaldehyde was synthesized (yield 34%).

4- (9,10-bis-biphenyl-2-yl-6-bromo-anthracen-2-yl) -benzaldehyde (0.80 g, 1.20 mmol) and N-phenyl-1,2-phenylene To diamine (0.22 g, 1.20 mmol), 50 ml of toluene and 10 ml of acetic acid were added and refluxed. After reacting for 2 days, the mixture was cooled to room temperature, the solid formed was filtered, separated by column chromatography, and recrystallized with ethanol and chloroform to synthesize the compound represented by Chemical Formula 1-14 (0.45 g, yield 45%).

The analysis results of this compound are as follows.

Melting point 417.7 ° C .; MS [M + H] 1231.

Example 6

(Production of Compound Represented by Formula 3-2)

In 9,10-dioxo-9,10-dihydro-anthracene-2-carbaaldehyde (1.63 g, 6.9 mmol), 1.27 g (6.9 mmol) of N-phenyl-1,2-phenylenediamine (1.27 g, 6.90 mmol) was added to 80 ml of toluene and 10 ml of acetic acid and refluxed for 12 hours. The solvent was removed, ethanol was poured and crystallized, followed by filtration to obtain a benzimidazole compound (2- (1-phenyl-1H-benzoimidazol-2-yl) -anthraquinone, 1.14 g, yield 41%).

2-bromobiphenyl (1.46 g, 1.1 ml, 6.25 mmol) was dissolved in tetrahydrofuran (50 ml) and tertiary-butyllithium (8.3 ml, 1.5 M pentane solution) was added slowly at -78 deg. 2- (1-phenyl-1H-benzoimidazol-2-yl) -anthraquinone (1.00 g, 2.50 mmol) synthesized above was slowly added to the reaction, followed by stirring at room temperature for 4 hours. The reaction was poured into 2N hydrochloric acid solution and ethyl ether mixture and stirred for 1 hour. The solid compound was filtered off and dried to give 9,10-bis [biphenyl-2-yl-2 (1-phenyl-1H-benzoimidazol-2-yl)]-9,10-dihydro-anthracene-9, 10-dialol (1.00 g, yield 57%) was obtained.

Dialcohol (0.70 g, 1.00 mmol) was dispersed in 60 mL of acetic acid under a nitrogen atmosphere, followed by addition of potassium iodine (1.66 g, 10 mmol) and sodium hypophosphite hydrate (1.66 g, 15.7 mmol), followed by stirring for 3 hours. It was. After cooling to room temperature, the mixture was filtered, washed with water and methanol, and dried in vacuo to obtain a compound (0.45 g, yield 67%) as a pale yellow chemical formula 3-2.

The analysis results of this compound are as follows.

Melting point 270.0 ° C .; 1 H NMR (300 MHz, CDCl ₃ ) 7.86 (d, 1H), 7.75 (dd, 1H), 7.70 (s, 1H), 7.63-7.48 (m, 8H), 7.42-7.0 (m, 12H), 6.92- 6.81 (m, 9 H), 6.63 (d, 2 H); MS [M + H] 675.

Example 7

(Manufacture of organic light emitting element)

A glass substrate coated with a thin film of ITO (indium tin oxide) at a thickness of 1500 Å was placed in distilled water in which detergent was dissolved and ultrasonically cleaned. Fischer Co., Ltd. product was used as a detergent, and distilled water filtered secondly was used as a filter of Millipore Co., Ltd. product. After washing ITO for 30 minutes, ultrasonic washing was repeated 10 times with distilled water twice. After the distilled water was washed, ultrasonic cleaning with a solvent such as isopropyl alcohol, acetone, methanol, dried and then transferred to a plasma cleaner. In addition, the substrate was cleaned for 5 minutes using an oxygen plasma, and then the substrate was transferred to a vacuum evaporator.

Hexanitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode to form a hole injection layer. NPB (600 kV), which is a material for transporting holes, was vacuum deposited thereon, and the compound represented by Chemical Formula j serving as a light emitting layer was vacuum deposited to a thickness of 100 kPa. The compound of Chemical Formula 1-2, which serves to inject and transport electrons on the light emitting layer, was vacuum deposited to a thickness of 200 kPa to complete the formation of a thin film of the organic material layer. Lithium fluoride (LiF) and aluminum having a thickness of 2500 kPa were deposited on the electron injection and transport layer sequentially to form a cathode. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at the deposition rate of 3-7 Å / sec.

As a result of applying a forward electric field of 4.04 V to the electroluminescent device manufactured above, a blue spectrum of 184 nit brightness corresponding to x = 0.16 and y = 0.11 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

Example 8

(Manufacture of organic light emitting element)

Hexitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode as in Example 7 to form a hole injection layer. NPB (600 kPa), which is a material for transferring holes, was vacuum-deposited thereon, and the compound represented by Chemical Formula 1 serving as a light emitting layer was vacuum deposited to a thickness of 200 kPa. The compound represented by Chemical Formula 2-2, which serves to inject and transport electrons on the light emitting layer, was vacuum deposited to a thickness of 200 kPa to complete the formation of a thin film of the organic material layer. Lithium fluoride (LiF) and aluminum having a thickness of 2500 kPa were deposited on the electron injection and transport layer sequentially to form a cathode. In the above process, the deposition rate of organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at a deposition rate of 3-7 Å / sec.

As a result of applying a forward electric field of 4.63 V to the electroluminescent device manufactured above, a blue spectrum of 226 nit brightness corresponding to x = 0.16 and y = 0.19 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

Example 9

(Manufacture of organic light emitting element)

Hexitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode as in Example 7 to form a hole injection layer. NPB (600 kV), which is a material for transferring holes, was vacuum deposited thereon, and the compound represented by Chemical Formula j serving as a light emitting layer was vacuum deposited to a thickness of 200 kPa. The compound represented by Chemical Formula 1-4, which serves to inject and transport electrons on the light emitting layer, was vacuum deposited to a thickness of 200 kPa to complete the formation of a thin film of the organic material layer. Lithium fluoride (LiF) and aluminum having a thickness of 2500 kPa were deposited on the electron injection and transport layer sequentially to form a cathode. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at the deposition rate of 3-7 / sec.

As a result of applying a forward electric field of 6.16 V to the electroluminescent device manufactured above, a blue spectrum of 175 nit brightness corresponding to x = 0.16 and y = 0.12 was observed based on 1931 CIE color coordinate at a current density of 10 mA / cm 2. It became.                     

Example 10

(Manufacture of organic light emitting element)

Hexitrile hexaazatriphenylene was thermally vacuum deposited to a thickness of 500 kPa on the prepared ITO transparent electrode as in Example 7 to form a hole injection layer. NPB (600 kPa), which is a material for transporting holes, was vacuum-deposited thereon, and the compound represented by Chemical Formula k serving as a light emitting layer was vacuum deposited to a thickness of 200 kPa. The compound represented by Chemical Formula 3-2, which serves to inject and transport electrons on the emission layer, was vacuum deposited to a thickness of 200 kPa to complete the formation of a thin film of the organic layer. Lithium fluoride (LiF) and aluminum having a thickness of 2500 kPa were deposited on the electron injection and transport layer sequentially to form a cathode. In the above process, the deposition rate of the organic material was maintained at 1 Å / sec, the lithium fluoride was 0.2 Å / sec, and the aluminum was maintained at the deposition rate of 3-7 Å / sec.

As a result of applying a forward electric field of 5.17 V to the electroluminescent device manufactured above, a blue spectrum of 124 nit brightness corresponding to x = 0.16 and y = 0.17 based on 1931 CIE color coordinate at a current density of 10 mA / cm 2 was observed. It became.

The novel material of the present invention is contained in an organic compound layer of an organic thin-film electroluminescence (organic EL) device which is an electroluminescent device, thereby improving luminous efficiency, lifetime, and low voltage driving.

Claims (17)

Compound represented by the following formula (1): [Formula 1]

In the formula of Formula 1, R ¹ and R ² are each independently or simultaneously a group derived from a hydrogen atom, an aliphatic hydrocarbon having 1 to 20 carbon atoms, phenyl, naphthyl, biphenyl, anthracenyl, aromatic heterocycle, or aromatic ring assembly, wherein R At least one of ¹ , and R ² is a group derived from phenyl, naphthyl, biphenyl, aromatic heterocycle or aromatic ring assembly, Ar is a group derived from phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocycle or an aromatic ring assembly, R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aliphatic hydrocarbon, substituted phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocyclic or aromatic ring assembly, X is NR ⁴ , sulfur atom or oxygen atom, R ⁴ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aliphatic hydrocarbon, phenyl, naphthyl, biphenyl, anthracenyl, or a group derived from an aromatic heterocycle or an aromatic ring assembly. Compound represented by the following formula (2): [Formula 2]

In the formula (2), R ¹ and R ² are each independently or simultaneously a group derived from a hydrogen atom, an aliphatic hydrocarbon having 1 to 20 carbon atoms, phenyl, naphthyl, biphenyl, anthracenyl, aromatic heterocycle, or aromatic ring assembly, wherein R At least one of ¹ , and R ² is a group derived from phenyl, naphthyl, biphenyl, aromatic heterocycle or aromatic ring assembly, Each Ar is a group derived from phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocyclic or aromatic ring assembly, Each X is NR ⁴ , a sulfur atom, or an oxygen atom, R ⁴ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aliphatic hydrocarbon, phenyl, naphthyl, biphenyl, anthracenyl, or a group derived from an aromatic heterocycle or an aromatic ring assembly. A compound represented by the following formula (3): [Formula 3]

In the formula (3), R ¹ and R ² are each independently or simultaneously a group derived from a hydrogen atom, an aliphatic hydrocarbon having 1 to 20 carbon atoms, phenyl, naphthyl, biphenyl, anthracenyl, aromatic heterocycle, or aromatic ring assembly, wherein R At least one of ¹ , and R ² is a group derived from phenyl, naphthyl, biphenyl, aromatic heterocycle or aromatic ring assembly, R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aliphatic hydrocarbon, substituted phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocyclic or aromatic ring assembly, X is NR ⁴ , sulfur atom or oxygen atom, R ⁴ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aliphatic hydrocarbon, phenyl, naphthyl, biphenyl, anthracenyl, or a group derived from an aromatic heterocycle or an aromatic ring assembly. Compound represented by the following formula (4): [Formula 4]

In the formula (4), R ¹ and R ² are each independently or simultaneously a group derived from a hydrogen atom, an aliphatic hydrocarbon having 1 to 20 carbon atoms, phenyl, naphthyl, biphenyl, anthracenyl, aromatic heterocycle, or aromatic ring assembly, wherein R At least one of ¹ , and R ² is a group derived from phenyl, naphthyl, biphenyl, aromatic heterocycle or aromatic ring assembly, Each X is NR ⁴ , a sulfur atom, or an oxygen atom, R ⁴ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aliphatic hydrocarbon, phenyl, naphthyl, biphenyl, anthracenyl, or a group derived from an aromatic heterocycle or an aromatic ring assembly. A compound represented by the following formula (5): [Formula 5]

In the formula (5), R ¹ and R ² are each independently or simultaneously a group derived from a hydrogen atom, an aliphatic hydrocarbon having 1 to 20 carbon atoms, phenyl, naphthyl, biphenyl, anthracenyl, aromatic heterocycle, or aromatic ring assembly, wherein R At least one of ¹ , and R ² is a group derived from phenyl, naphthyl, biphenyl, aromatic heterocycle or aromatic ring assembly, Ar is a group derived from phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocycle or an aromatic ring assembly, X is NR ⁴ , sulfur atom or oxygen atom, R ⁴ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aliphatic hydrocarbon, phenyl, naphthyl, biphenyl, anthracenyl, or a group derived from an aromatic heterocycle or an aromatic ring assembly. An organic selected from the group consisting of a compound represented by formula 1, a compound represented by formula 2, a compound represented by formula 3, a compound represented by formula 4, and a compound represented by formula 5 below An organic light emitting device comprising an organic compound layer containing a compound: [Formula 1]

[Formula 2]

[Formula 3]

[Formula 4]

[Formula 5]

In the formula 1, 2, 3, 4, and 5, R ¹ and R ² are each independently or simultaneously a group derived from a hydrogen atom, an aliphatic hydrocarbon having 1 to 20 carbon atoms, phenyl, naphthyl, biphenyl, anthracenyl, aromatic heterocycle, or aromatic ring assembly, wherein R At least one of ¹ , and R ² is a group derived from phenyl, naphthyl, biphenyl, aromatic heterocycle or aromatic ring assembly, Ar is a group derived from phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocycle or an aromatic ring assembly, R ³ is a hydrogen atom, an alkyl group having 1 to 6 carbon atoms or an aliphatic hydrocarbon, substituted phenyl, naphthyl, biphenyl, anthracenyl, or an aromatic heterocyclic or aromatic ring assembly, X is NR ⁴ , sulfur atom or oxygen atom, R ⁴ is a hydrogen atom, an alkyl group having 1 to 7 carbon atoms or an aliphatic hydrocarbon, phenyl, naphthyl, biphenyl, anthracenyl, or a group derived from an aromatic heterocycle or an aromatic ring assembly. The method of claim 6, At least one organic compound layer is positioned between an anode for injecting holes and a cathode for injecting electrons. The method of claim 6, The organic light emitting device of the organic compound layer is an electron injection and transport layer having an electron injection and transport function. The method of claim 6, The organic light emitting device of the organic compound layer is an electron injection and light emitting layer having an electron injection and light emitting function. The method of claim 6, The organic light emitting device of the organic compound layer is an electron transport and light emitting layer having an electron transport and light emitting function. The method of claim 6, The organic light emitting device comprises a substrate, an anode, a hole injection layer, a hole transport layer, an organic light emitting layer, an electron transport layer, and a cathode from below, the compound represented by the formula (1), the compound represented by the formula (2), An organic light-emitting device in which at least one organic compound selected from the group consisting of a compound represented by the compound represented by Chemical Formula 4, and a compound represented by Chemical Formula 5 is contained in the organic light emitting layer and the electron transport layer . The method of claim 6, An organic light emitting device in which the organic compound layer contains a compound of Formula 1a or 3a: [Formula 1a] [Formula 3a]

In the formula of Formula 1a and Formula 3a, Ar ₁ , Ar ₂ , and Ar ₃ each independently or simultaneously represent an aromatic hydrocarbon, and R ⁵ is a hydrogen atom and an alkyl group having 1 to 4 carbon atoms, an aromatic hydrocarbon or a heterocyclic compound. The method of claim 6, An organic light emitting device is a compound represented by Formula 1 is a compound selected from the group consisting of compounds of Formula 1-1 to Formula 1-16: [Formula 1-1] [Formula 1-2]

[Formula 1-3] [Formula 1-4]

[Formula 1-5] [Formula 1-6]

[Formula 1-7] [Formula 1-8]

[Formula 1-9] [Formula 1-10]

[Formula 1-11] [Formula 1-12]

[Formula 1-13]

[Formula 1-14]

[Formula 1-15]

[Formula 1-16]

. The method of claim 6, An organic light emitting device is a compound represented by Formula 2 is a compound selected from the group consisting of compounds of Formula 2-1 to Formula 2-5: [Formula 2-1]

[Formula 2-2]

[Formula 2-3]

[Formula 2-4]

[Formula 2-5]

. The method of claim 6, An organic light emitting device is a compound represented by Formula 3 is a compound selected from the group consisting of compounds of the following formula 3-1 to formula 3-9: [Formula 3-1] [Formula 3-2]

[Formula 3-3] [Formula 3-4]

[Formula 3-5] [Formula 3-6]

[Formula 3-7] [Formula 3-8]

[Formula 3-9]

. The method of claim 6, An organic light emitting device is a compound represented by Formula 4 is a compound selected from the group consisting of compounds of the following formula 4-1 to formula 4-5: [Formula 4-1] [Formula 4-2]

[Formula 4-3] [Formula 4-4]

[Formula 4-5]

. The method of claim 6, An organic light emitting device is a compound represented by Formula 5 is a compound selected from the group consisting of the compound of Formula 5-1 to Formula 5-5: [Formula 5-1]

[Formula 5-2]

[Formula 5-3]

[Formula 5-4]

[Formula 5-5]

.

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